Processes for breaking petroleum emulsions with dicarboxy acid esters of sulfated oxyalkylated alkyl phenolformaldehyde resins



United States Patent 10 Claims. Cl. 252-335 This application is adivision of our copending application Serial No. 818,562, filed June 8,1959, now Patent No. 3,108,087, issued October 22, 1963, which was acontinuation-impart of our application Serial No. 632,- 427, filedJanuary 4, 1957, now abandoned.

This invention, in general, relates to new compositions of matter andtheir use in the treatment of emulsions of mineral oils and water, suchas petroleum emulsions commonly encountered in the production, handlingand refining of crude mineral oil.

Petroleum emulsions are, in general, of the water-in-oil type whereinoil acts as the continuous phase for dispersal of the finely-dividedparticles of naturally occurring waters or brines. These emulsions areoften extremely stable and will not resolve into the oil and watercomponents even on long standing. The emulsions obtained from producingWells and from the bottom of crude oil storage tanks are commonlyreferred to as cut oil, emulsified oil, bottom settlings and B.S.. It isalso to be understood that water-in-oil emulsions may occurartificially, resulting from any one or more of numerous operationsencountered in various industries.

One type of process involves subjection of emulsions of the water-in-oiltype to the action of a deemulsifying agent of the kind hereinafterdescribed, thereby causing the emulsion to resolve and stratify into itscomponent parts of oil and water or brine after emulsion has beenallowed to stand in a relatively quiescent state.

One object of our invention is to provide novel and economical efiectiveprocesses for resolving emulsions of the character referred to intotheir component parts of oil and water or brine.

' Another object is to provide novel reagents which are surface-activein order to enable their use as deemulsifiers or for such uses wheresurface-active characteristics are necessary or desirable. Other objectswill appear hereinafter.

In accordance with the invention, the crude oil deemulsifying agents aredicarboxy acid esters of sulfated oxyalkylated alkyl phenol-formaldehyderesins. The phenol-formaldehyde resins are the alkali-insoluble reactionproducts of formaldehyde with a difunctional monoalkyl phenol, the alkylgroup having between 4-15 carbons, inclusive, preferably 5-15 carbons,and being in the ortho or para position. Dlalkyl monofunctional phenolsare not suitable for compositions of this invention, but amounts up to25% dialkyl phenol in the monoalkyl phenol reactant may be tolerated.The weight ratio of the lower alkylene oxide, e.g., ethylene oxide ormixtures of ethylene oxide and 1,2-propylene oxide, to thephenolformaldehyde condensation product will, for most applications,fall between about 1:2 and 15:1, respectively, preferably the range of1:2 to 9: 1.

Where both ethylene oxide and propylene oxide are used to oxyalkylatethe phenol-formaldehyde condensation product, they may be reacted as amixture of oxides to give heterogeneously mixed oxypropylene andoxyethylene groups in the oxyalkylene chains. Alternatively, one of theoxides may be reacted with the condensation product first, then theother. In this manner, the oxyalkylene chains are composed ofpolyoxypropylene groups attached to the phenolic nuclei of thecondensation product and terminal poloxyethylene groups added upon" thepolyoxypropylene groups, or vice versa, wherein the polyoxyethylenegroups are attached to the phenolic nuclei and the polyoxypropylenegroups are in the terminal positions.

There is an advantage to having the terminal group of the oxyalkylenechains as an oxyethylene group because the latter has a primary hydroxylgroup. A terminal oxypropylene group, on the other hand, has a secondaryhydroxyl group, which is more difficult to sulfate or esterify than theprimary hydroxyl group. Simultaneous reaction of a mixture of bothethylene and propylene oxide probably yields an oxyalkylated producthaving both types of terminal hydroxyl groups.

PHENOL-FORMALDEHYDE CONDENSATION The phenol-formaldehyde condensationproducts are prepared by reacting formaldehyde or a substance whichbreaks down to formaldehyde under the reaction conditions, e.g.,paraformaldehyde and trioxane, and a difunctional monoalkyl phenol byheating the reactants in the presence of a small amount of an acidcatalyst such as sulfamic acid under substantially anhydrous conditionsexcepting the water produced during the reaction. The aqueous distillatewhich begins to form is collected and removed from the reaction mixture.After several hours of heating at temperatures slightly above theboiling point of Water, the mass becomes viscous and is permitted tocool to about to C. At this point a suitable hydrocarbon fraction isadded, and heating is resumed. Further aqueous distillate begins to formand heating is continued for an additional number of hours until atleast about one mol of aqueous distillate per mol of reactants has beensecured. The product is permitted to cool to yield the phenolformaldehyde condensation product in a hydrocarbon solvent. Themolecular weight of these intermediate condensation products cannot beascertained with certainty, but we would approximate that the resinsemployed herein should contain about 4 to 15, preferably 4 to 10,phenolic nuclei per resin molecule. The solubility of the condensationproduct in hydrocarbon solvents such as S0 extract would indicate thatthe resins are linear type polymers, thus distinguishing them from themore common phenol-formaldehyde resins of the cross-linked type.

The phenol component of our phenol-formaldehyde resins is entirely orprincipally a difunctional phenol one having only two of the threenormally reactive orthoand para-positions available for reaction withthe formaldehyde. These phenols are mono-alkyl phenols with the alkylgroup in the para or ortho position having up to about 15 carbons.Phenols suitable for our invention are difunctional, mono-alkyl phenolshaving straight chain or branch chain alkyl groups of 4-15 carbons,preferably 5-15 carbons. Examples of the phenolic component include suchpreferred phenols as p-n-butyl phenol, p-tertiary butyl phenol, p-amylphenol, p-tertiary hexyl phenol, p-tertiary octyl (1,1,3,3-tetramethylbutyl-l) phenol, pnonyl phenol, p-dodecyl phenol, a crude alkyl phenolcontaining at least about 90% p-nonyl phenol and up to 10% dinonylphenol, and others including mixtures of orthoand/or para-monoalkylphenols and crude alkylate phenols containing at least 75% difunctionalalkyl phenols with the remainder being primarily monofunctional phenols.

This aspect of the invention is illustrated in the following examplesbut is not limited thereto. The parts are by weight.

Example A In a three-necked reaction flask provided with means ofmechanical stirring and a return condenser system permitting the removalof any aqueous phase formed in the course of reaction, there is added1500 parts of a crude alkylate phenol which comprises about 90% of anundistillecl p-nonyl phenol containing approximately 10% ofdinonylphenol, 225 parts paraformaldehyde and 3 parts sulfamic acidwhich is present as a catalyst in the reaction. The reaction mass isheated, and at 108 C. an aqueous distillate begins to form. After threehours heating at approximately 110 C. the mass becomes quite viscous andis permitted to cool to about 100 C. At this point 600 parts of Sextract is added, and heating is resumed. Again at 110 C. furtheraqueous distillate begins to form, and heating is continued for anadditional three hours, or until approximately 141 cc. of aqueousdistillate has been secured at a maximum temperature of 212 C. Theproduct is permitted to cool to yield the finished phenol-formaldehyderesin in the hydrocarbon solvent.

Example B In a manner similar to Example A, 1000 parts of the crudealkylate phenol, 120 parts of paraformaldehyde and 2 parts sulfamic acidwere heated 2 hours at 105- 110 C. to permit reaction of the phenol andformaldehyde under conditions minimizing formaldehyde loss. Attemperatures aboue 110 C. vigorous reaction sets in which must becontrolled by cooling. After about 27 parts of aqueous distillate havebeen secured, the reaction comes under control and becomes exceedinglyviscous. At this point the resin is cooled to 105 C., and 400 parts ofS0 extract is added. Heating is continued for an additional three hours,or until a total of about 75 parts of aqueous distillate have beenremoved at maximum temperature of 212 C. to yield the finishedphenolformaldehyde resin in the hydrocarbon solvent.

Example C In a manner similar to Examples A and B, 1000 parts of thecrude alkylate phenol, 90 parts paraformaldehyde and 2 parts sulfamicacid are carefully reacted at temperatures of 100-110 C. When thereaction mass becomes quite viscous, the reaction is permitted to cool,and 400 parts of S0 extract are added. Heating is resumed for anadditional hour, or until a total of 55 parts of aqueous distillate havebeen secured at maximum temperature of 213 C. to yield the finishedphenol formaldehyde resin in the hydrocarbon solvent.

Example D To a vessel having a stirrer and a return condenser systempermitting the removal of the aqueous phase of the distillate is added1400 parts of p-tertiary butyl phenol, 310 parts of paraformaldehyde andparts of sulfamic acid as catalyst. The mass is heated, and at about105-110 C. an aqueous distillate begins to form. After heating for threehours at l05-110 C., the mass becomes viscous and is permitted to coolto 95l00 C. About 4 500 parts of a suitable hydrocarbon fraction isadded and heating is resumed. At l05110 C. further distillate begins toform and heating is continued for an additional three hours untilapproximately 140 cc. of aqueous distillate is obtained. The product iscooled to yield the phenol-formaldehyde resin solution in thehydrocarbon vehicle.

Example E Following the technique of Example D, an equivalent amount ofp-teritary hexyl phenol is substituted for the p-tertiary butyl phenolof Example D.

In the preceding examples, sulfamic acid has been used as the acidcatalyst to assist in the condensation reaction. Other suitableequivalent acids which may be used in place of sulfamic acid are mineralacids such as sulfuric acid, hydrochloric acid, phosphoric acid, etc.

As stated heretofore, intermediate phenol-formaldehyde resin shouldcontain a minimum of about 4 phenolic nuclei and should not exceed about15 phenolic nuclei. It is extremely difficult, if not impossible, toaccurately determine the molecular weight of the intermediate resinproducts. However, it is believed that the resin of Example A containsabout 10 phenolic nuclei per resin molecule, Example B, about 7 phenolicnuclei, and Example C, about 4 phenolic nuclei per resin molecule.

Oxyalkylation 0 the condensation products Having prepared theintermediate phenol-formaldehyde products, the next step is theoxyalkylation with cyclic xides having 2-3 carbons of the condensationproductsoxyalkylation occurring at the OH group of the phenol to provideoxyalkylene group on the phenolic nuclei. This is achieved by mixing theintermediate phenolformaldehyde condensation product in a hydrocarbonsolvent with a small amount of a suitable catalyst in an autoclave. Thecondensation product is heated above 100 C., and ethylene oxide or amixture of ethylene oxide and 1,2-propylene oxide, either as a mixtureor by sequential addition of first either the propylene oxide or theethylene oxide and then the other oxide, is charged into the autoclaveuntil the pressure is in the vicinity of -100 psi.

The reaction mixture is gradually heated until an exothermic reactionbegins. The external heating is then removed, and alkylene oxide isadded at such a rate that the temperature is maintained between about150- 160 C. at a pressure range of to psi. After all of the alkyleneoxide has been added, the temperature is maintained for an additional 10to 20 minutes to assure substantially complete reaction of the alkyleneoxide. The resulting product is the alkylene oxide adduct of an alkylphenol formaldehyde condensation product, in which the weight ratio ofthe oxide to the condensation product is between about 2:3 and 15:1,respectively, preferably 2:3 to 9:1. The molecular weight of theoxyalkylated phenol formaldehyde condensation products of this inventionrange from as low as about 1100 to as high as about 50,000. In theproducts containing both oxyethylene and oxypropylene groups, the ratioof the two will ordinarily vary from the lower limit of no oxypropylenegroups (totally oxyethylated) to an oxypropylone to oxyethylene weightratio not exceeding about 25:1.

Some preferred embodiments of the oxyalkylated, alkyl phenolformaldehyde condensation products and methods of their preparation areillustrated in the following examples wherein all parts are by Weightunless otherwise stated, but the invention is not limited thereto.

Example F In an autoclave having a two-liter capacity equipped with ameans of external electric heating, internal cooling coils andmechanical agitation, there is charged 950 parts of the resin solutionof Example A, and 1.5 parts of sodium hydroxide. Into a transfer bombthere is introduced 575 parts ethylene oxide. The resin is heated to 135C., and the ethylene oxide is charged into the reactor until reactorpressure is 80 psi. The reaction mixture is gradually heated until anexothermic reaction begins to take place. The external heating is thenremoved and ethylene oxide is then added at such a rate that thetemperature is maintained between 150160 C. with a pressure range of 80to 100 psi. After approximately two hours all of the oxide has beenadded to the autoclave, and the temperature is maintained for anadditional minutes to make certain that the unreacted oxide is reducedto a minimum. The resulting product is the ethylene oxide adduct of aphenol-formaldehyde resin, in which the weight ratio of oxide to resinby weight is 2 to 3. The oxyalkylated phenol formaldehyde condensationproduct had a hydroxyl equivalent weight of about 620 and containedabout ten oxyalkylene chains per resin molecule.

Example G In a manner similar to Example F, the ethylene oxide adduct ofthe resin of Example B was prepared in which the ratio of ethylene oxideto resin was 1 /2 to 1 by weight. The oxyalkylated phenol-formaldehydecondensation product had a hydroxyl equivalent weight of about 840 andcontained about four oxyalkylene chains per resin molecule.

Example H In the same facilities as used in Example F, there is charged172 parts of the resin solution of Example A and 1 part of sodiumhydroxide. Into a transfer bomb there is introduced 250 parts by weightof ethylene oxide and 250 parts of propylene oxide. The intermediate isheated to 135 C., and the mixed oxides are charged into the reactoruntil the reactor pressure is 80 p.s.i. The reaction conditions fromhere on are identical with those employed in Example F. The resultingproduct is the mixed oxide adduct of a phenol-formaldehyde resin inwhich the ratio of oxide to resin by weight is approximately 4 to 1. Theoxyalkylated phenol formaldehyde condensation product had a hydroxylequivalent weight of about 1400 and contained about ten oxyalkylenechains per resin molecule.

Example J In a manner similar to Example H, using a 1 to 1 by weightratio of ethylene oxide and propylene oxide, a mixed oxide adduct of theresin of Example C was prepared in which the ratio of oxide to resin was6 to 1. The oxyalkylated phenol-formaldehyde condensation product had ahydroxyl equivalent weight of about 1400 and contained about fouroxyalkylene chains per resin molecule.

Example K In a manner similar to Example H using a 1 to 3 by weightratio of ethylene oxide to propylene oxide, a mixed oxide adduct of theresin of Example C was prepared in which the ratio of oxide to resin was6 to 1. The oxyalkylated phenol-formaldehyde condensation product had ahydroxyl equivalent weight of about 1500 and contained about fouroxyalkylene chains per resin molecule.

Example L In a manner similar to Example H using a 1 to 3 by weightratio of ethylene oxide to propylene oxide, a mixed oxide adduct of theresin of Example B was prepared in which the ratio of oxide to resin was2 to 1.

Example M In a manner similar to Example H using a 3 to 1 by weightratio of ethylene oxide to propylene oxide, a mixed oxide adduct of theresin of Example A was prepared in which the ratio of oxide to resin was1 to 1. The oxyalkylated phenol-formaldehyde condensation product had ahydroxyl equivalent weight of about 700 and contained ten oxyalkylenechains per resin molecule.

6 Example N In a manner similar to Example F there is prepared apropylene oxide adduct of the resin of Example A in which the ratio ofpropylene oxide to resin by weight is 1 to 1. The oxypropylated phenolformaldehyde resin was then reacted further with ethylene oxide untilthe finished product contained 10% by weight of ethylene oxide. Theoxyalkylated phenol-formaldehyde condensation product had a hydroxylequivalent weight of about 750 and contained about ten oxyalkylenechains per resin molecule.

Example 0 In a manner similar to Example N a propylene oxide adduct ofthe resin of Example C was prepared in which the ratio of propyleneoxide to resin was 6 to 1 by weight. Ethylene oxide was then added tothis oxypropylated phenol-formaldehyde resin until the finished productcontained 20% by weight of ethylene oxide. The oxyalkylated phenolformaldehyde condensation product had a hydroxyl equivalent weight ofabout 1200 and contained about four oxyalkylene chains per resinmolecule.

Example P In a manner similar to Example N a propylene oxide adduct ofthe resin of Example A was prepared in which the ratio of propyleneoxide to resin was 9 to 1 by weight. This oxypropylated phenolformaldehyde resin was then further reacted with ethylene oxide untilthe finished material contained 5% by weight of ethylene oxide. Theoxyalkylated phenol-formaldehyde condensation product had a hydroxylequivalent weight of about 1400 and contained about ten oxyalkylenechains per resin molecule.

Example Q In a manner similar to Example N a propylene oxide adduct ofthe resin of Example C was prepared in which the ratio of propyleneoxide to resin was 2 to 1 by weight. This oxypropylatedphenol-formaldehyde resin was then further reacted with ethylene oxideuntil the finished material contained 30% by weight of ethylene oxide.The oxyalkylated phenol-formaldehyde condensation product has a hydroxylequivalent weight of about 1200 and contained about four oxylalkylenechains per resin molecule.

Example R In a manner similar to Example H, the mixed propylene oxideand ethylene oxide adduct (weight ratio 6: 1, respectively) of the resinof Example D is prepared in which the weight ratio of oxide tocondensation product is 4 to 1.

Example S In a manner similar to Example F, the mixed propylene oxideand ethylene oxide adduct (weight ratio 3: 1, respectively) of thecondensation product of Example E is prepared in which the weight ratioof oxide to condensation product is 2 to 1.

SULFATION AND ESTERIFICATION OF THE OXY- ALKYLATED CONDENSATION PRODUCTSThe next and final step in the preparation of the compositions of ourinventions is esterification with dicarboxy acids and sulfation of theoxyalkylated alkyl phenolformaldehyde condensation products. In someinstances, the sulfation and dicarboxy acid esterification steps can becarried out simultaneously, and in other instances it it preferred, andsometimes even essential, that the dicarboxy acid esterification step becarried out prior to the sulfation step. When using a dicarboxy acid,the esterification reaction should precede the sulfation reaction with,for example, sulfamic acid. When a dicarboxy acid anhydride is employedfor esterification, the sulfation and esterification reactions may becarried out simultaneously, if desired.

The dicarboxy acid esterification step is achieved heating the oxylatedresin and dicarboxy acid or anhydride thereof in a suitable hydrocarbonsolvent to a temperature sufficient to produce esterification, at leastabove the boiling point of water. The aqueous distillate is collectedand removed from the reaction vessel. The same condition are applicablewhen sulfation and esterification are carried out simultaneously or whensulfation precedes esterification. Care must be taken, however, that thetemperature he held below that at which the reactants are decomposed orotherwise detrimentally affected by the sulfating composition. In someinstances, the reaction can be carried out advantageously under vacuumwhere the temperature must be kept below 100 C. with the particularsulfating agent used. However, we prefer to use sulfamic acid as thesulfating agent in simultaneous sulfation and esterification because thereactants may be heated substantially above 100 C. without detrimentaleffect on the reactants by the su-lfamic acid. In general, the dicarboxyacid esterification proceeds more rapidly and efficiently attemperatures above 100 C. The sulfation reaction is described in moredetail below. The esterification reaction is stopped when sufficientaqueous distillate has been collected which is equivalent toesterification of one carboxyl group of the dicarboxy acid or anhydride,or somewhat prior thereto. The reaction should not proceed substantiallybeyond this point because the final dicarboxy acid esters of sulfatedoxyalkylated alkyl phenol formaldehyde resins should have essentiallyone free carboxyl group per dicarboxy acid radical. The degree ofesterification with the dicarboxy acid may range from compositions inwhich only one hydroxyl group per sulfated oxyalkylated phenolformaldehyde molecule is esterfied to total esterification of theunsulfated hydroxyl groups of the oxyalkylated resin.

The degree of sulfation may range from compositions in which only onehydroxyl group per esterified oxyalkylated phenol-formaldehyde resinmolecule is sulfated to total sulfation of the unesterfied hydroxylgroups of the oxyalkylated resin. The preferred sulfating reagent issulfamic acid because of the ease and convenience in handling in plantoperations. The sulfo groups, however, can be introduced by other meanssuch as sulfuric acid, sulfur trioxide, etc. With the use of theselatter reagents it is essential that the temperature conditions ofreaction be lower and be carefully controlled so that the sulfationreaction proceeds without decomposition of the oxyalklyatedphenol-formaldehyde resin. Other than the careful control of temperatureconditions and sulfation at lower temperatures, the reaction conditionsemployed for the preparation of the sulfo derivatives with thelastmentioned sulfating agents are substantially identical to those forsulfation with sulfamic acid. The sulfation is accomplished by heatingand stirring a mixture of the oxyalkylated phenol-formaldehyde resin andthe sulfating reagent. The mixture is heated in the vicinity of about120150 C. in the case of sulfamic acid and held at that point forapproximately two hours under agitation to complete the sulfationreaction. The sulfated product so prepared is then cooled below about100 C., at which point a suitable hydrocarbon extract is added to yielda solution of the finished product. It has been observed that increasingthe number of sulfo groups per molecule results in substantiallyincreased viscosity of the sulfated product.

The dicarboxy acids are aliphatic, cycloaliphatic or aromaticpolycarboxy acids. In some instances, we prefer dicarboxy acids having2-10 carbons and in other instances acids of higher molecular weight,having at least 36 carbons, such dimerized abietic acid, dimerizedlinoleic acid, dimerized linoleic acid, etc., are employed. Polycarboxyacids or anhydrides thereof which may be used in the esters of ourinvention include oxalic, maleic, malonic, succinic, diglycolic, adipic,azelic, sebacic, fumaric,

tartronic, malic, camphoric, tartaric, phthalic, and terephthalic acidsor anhydrides, VR1 polymeric acid, dimerized abietic acid, dimerizedlinoleic acid or dimerized linoleic acid, amoung others, including thefollowing dimerized drying oil acids.

Every dimer acid is essentially d'ilinoleic acid and is a polymer madeby polymerizing an unsaturated fatty acid containing at least twononconjugated double bonds. Such acids may also be described as polymerdrying oil acids. The term drying oil acid is used herein to mean anunsaturated fatty acid containing at least two double bonds and at lastsix carbon atoms. The polymer acids employed for the purpose of theinvention preferably consist predominantly of dimer acids but maycontain trimers and higher polymers. The preferred polymer acids arethose containing 12 to 40 carbon atoms and especially the polymers ofthe drying oil acids of the linoleic acid series, including, forexample, the polymers of sorbic acid, geranic acid, palmitolic acid,linoleic acid and humoceric acid. It will be understood that thesepolymers may include cogeneric mixtures of polycarboxy acids.

A number of these polymers acids are available as byproduct materials.Thus, one source of the polymeric acids suitable for the purposes ofthis invention is the still residue if the dry distillation of castoroil in the presence of sodium hydroxide. VR-l acid is an acid of thistype.

VR-l acid is a mixture of polybasic acids, with an average molecularweight of about 1,000. It has an average of slightly more than twocarboxylic acid groups per molecule. It is a by-product acid, and is adark amber, rather viscous liquid. A typical sample of VR-l acid gavethe following analysis:

Acid number 150 Iodine number 36 Saponification number 172Unsaponifiable matter percent 3.7, 3.5 Moisture content do 0.86

The dicarboxy acid esters of the sulfated oxyalkylated resins may beused in the acid form or any suitable form wherein the ionizablehydrogen of the sulfate group is replaced by a metal or other suitablecation. In many instances, it is desirable that the compositions be inthe form of salts of alkali metals or the ammonium salt. These salts maybe obtained by reacting the acidic product with a metallic hydroxide,ammonia, or an organic base, or an alkaline salt of one of these.Suitable bases and salts include ammonium, sodium and potassiumhydroxides and carbonates, as well as bicarbonates; aqueous ammonia; andamines such as lower alkyl amines, lower alkanol amines, and simple arylamines. Sulfamic acid as the sulfating reagent yields the ammonium salt.

The compositions of our invention are insoluble in water. For purposesherein, the sulfated and esterified oxyalkylated phenol-formaldehydecondenstation products of the character herein described are consideredto be water insoluble when, at equilibrium with distilled pure water at70 F., not more than 2 parts by weight dissolve per parts of water.These products are distinguished from water-soluble, detergent-typeresins of somewhat similar composition.

To provide the desired water insolubility, the hydrophilic-hydrophobicbalance of our compositions must be weighted on the hydrophobic side.Oxyethylene groups are considerably more hydrophilic than oxypropylenegroups. Noting that the alkyl phenol-formaldehyde resins, upon which ourcompositions are built, are per se water insoluble, there is a definitelimit to the amount of oxyethylation thereof in order to avoid reachinga state of water insolubility of our ultimate compositions throughexcessive oxyethylation.

The polycarboxy acid component also has a bearing on thehydrophilic-hydrophobic balance. In general, the

lower the molecular weight of the polycarboxy acid, the greater ishydrophilic nature. Polycarboxy acids having 36 or more carbons, such asdimerized linoleic or linolenic acids (which may contain minor amountsof higher polymers) dimerizer abietic acid, or VR-l polymer acid, aremuch more hydrophobic than polycarboxy acids having 2-10 carbons.

Accordingly, our compositions must have either sufficient oxypropylenegroups, or a higher molecular weight polycarboxy acid, or both, to makethe ultimate product water-insoluble within the meaning given supra.

Where ethylene oxide is the sole oxyalkylating agent, the weight ratioof ethylene oxide to alkyl phenol-formaldehyde condensation product willnot exceed about 2:1 nor be less than about 2:3, respectively, and thepolycarboxy acid will be a polycarboxy acid having at least 36 carbons,such as one of those described heretofore. Where the phenol-formaldehydecondensation products are oxyalkylated by a heterogeneous mixture of1,2- propylene oxide and ethylene oxide, or by the sequential additionof one oxide and then the other, the weight ratio of the oxides may varyfrom all ethylene oxide up to a ratio of propylene oxide to ethyleneoxide of 25:1 when the polycarboxy acid used to esterify theoxya'lkylene hydroxyl groups contains at least about 36 carbons. Whenthe polycarboxy acid contains 2-10 carbons, the oxyalkylene groupsshould have a weight ratio of oxypropylene groups to oxyalkylene groupswhich is not less than about 1:1 nor more than about 25:1, respectively.

The following examples will further illustrate the nature of thecompositions of this invention in preferred embodiments thereof, but theinvention is not limited to these examples.

Example I In a three-necked reaction flask provided with meansof'mechanical stirring and return condenser system permitting theremoval of any aqueous phase formed in the reaction, there is added 400parts by Weight of the oxyalkylated resin of Example Q, 20 parts byweight of diglycolic acid and 50 parts by weight of a suitablehydrocarbon fraction such as S extract. The reaction mass is heated, andat 200 C. an aqueous distillate begins to form. After approximately 45minutes of heating and a maximum temperature of 265 C., a total aqueousdistillate has been secured, which is equivalent to esterification ofone carboxyl group of the diglycolic acid. The reaction mass is cooledto 140 C. and 4 parts by weight of sulfamic acid are added and heatedfurther for 1 hour at 130140 C. To the cooled mass is added 225 parts byweight of S0 extract to yield a solution of the finished dibasic acidester of a sulfated oxyalkylated phenol-formaldehyde resin.

Example 11 In a manner similar to Example I, 400 parts of theoxyalkylated resin of Example 0, parts diglyco lic acid and 50 parts ofS0 extract are heated until 4.2 parts of an aqueous distillate have beensecured at a maximum temperature of 260 C. The product is cooled to 135C., 4 parts of sulfamic acid are added, and heating continued for 1additional hour. to cool, and 285 parts of S0 extract and 50 parts ofmethanol are added to yield the finished product.

Example III The product is permitted l 0 Example IV In a manner similarto Example I, parts of the oxyalkylated resin of Example F, 12 parts ofsulfamic acid, 12.5 parts of dilinoleic acid and 32 parts of S0 extractwere heated at l30140 C. for 4 hours to yield the sulfated ester. Aftercooling, 32 parts of isopropanol were added to yield the finishedproduct.

Example V In a manner similar to Example I, 400 parts of theoxyalkylated resin of Example H and 8 parts of sulfamic acid were heated2 hours at 135-445 C. At this point, 40 parts of maleic anhydride wereadded and the reaction mixture further heated for 4 hours to 130 C.

Example VI In a manner similar to Example I, 400 parts of theoxyalkylated resin of Example I, and 4 parts of sulfamic acid wereheated for 1 hour at -135 C. At this point, 40 parts maleic anhydridewere added and the temperature continued for 3 hours at 120-125 C. Aftercooling, 400 parts of S0 extract were added to yield the finishedproduct.

Example VII In a manner similar to Example I, 100 parts of theoxyalkylated resin of Example N, 12 parts sulfamic acid, 6 partsphthalic anhydride and 32 parts of S0 extract were heated to 130-140 C.for 4 hours. After cooling, 32 parts of isopropanol were added to yieldthe finished material.

Example VIII In a manner similar to Example I, 100 parts of theoxyalkylated resin of Example N, 10 parts of sulfamic acid, 18 parts ofdimerized abietic acid, and 40 parts of S0 extract are heated to aboutC. for 6 hours. After cooling, 150 parts of S0 extract are added.

Example IX In a manner similar to Example I, 200 parts of theoxyalkylated resin of Example G, 18 parts of sulfamic acid, 50 parts ofRohm & Haas VR-l polymeric acid having an average molecular weight ofabout 1000 and an average of about two carboxy groups per molecule, and75 parts of S0 extract are heated to about C. for 6 hours. Aftercooling, 250 parts of S0 extract are blended with the reaction product.

Among the suitable hydrocarbon vehicles which can be employed asreaction solvents is sulfur dioxide extract. This material is aby-product from the Edeleanu process of refining petroleum in which theundesirable fractions are removed by extraction with liquid sulfurdioxide. After removal of the sulfur dioxide a mixture of hydrocarbons,substantially aromatic in character, remains and is designated in thetrade as sulfur dioxide extract or S0 extract. Examples of othersuitable hydrocarbon vehicles are toluene, xylene, gas oil, diesel fuel,bunker fuel and coal tar solvents. The above cited examples of solventsare adaptable to azeotropic distillation as would also be any othersolvent which is immiscible with water, miscible with the reacting massand has a boiling point or boiling range in excess of the boiling pointof water.

DEEMULSIFICATION The compositions of this invention are surface-activeand are particularly suitable for the deemulsification of crude oilemulsions. Deemulsification is achieved by mixing the deemulsifyingagents of this invention, at a ratio in the approximate range of onepart of the deemulsifying agent to 2,00050,000 parts of the emulsion,and thereafter allowing the emulsion to remain in a relatively quiescentstate during which separation of the oil and water occurs. Thedeemulsifying agents of this invention may be used in conjunction withother deemulsifying agents from classes such as the petroleum sulfonatetype, of which naphthalene sulfonic acid is an example, the modifiedfatty acid type, the amine modified oxyalkylated phenol-formaldehydetype, and others.

The effectiveness of the compositions of this invention as deemulsifyingagents is illustrated in the following tests and data.

BOTTLE TESTING OF CRUDE OIL EMULSIONS The bottle testing of crude oilemulsions is conducted according to the following procedure: Freshsamples of the emulsion-breaking chemicals in organic solvent solutionare prepared in solutions. These solutions are made by accuratelydiluting 10 milliliters of the emulsionbreaking chemicals in 90milliliters of a mixture of equal parts of anhydrous isopropyl alcoholand an aromatic hydrocarbon such as xylene. The mixture is agitated welluntil the emulsion-breaking chemical is completely dissolved.

The equipment for running the crude oil emulsionbreaking test, inaddition to the foregoing 10% solutions, includes a set of six ouncegraduated prescription bottles, a funnel, a graduated 0.2 milliliterpipette, a thief pipette, a centrifuge, centrifuge tubes and athermometer. The graduated prescription bottles are filled to the 100milliliter mark with the crude oil emulsion to be tested, preferably asample which has been recently collected. If there is any free water inthe crude oil emulsion sample collected, it is bled off before thebottles are filled. Each bottle is inverted several times with the thumbover the opening of each bottle so that the bottle will be coated withan emulsion film.

By means of the 0.2 milliliter pipette, the prescribed volume of the 10%solution of the emulsion-breaking chemical is added to the emulsion inthe bottles. The bottles are then capped and given manual agitation fora predetermined number of counts. The number of counts are determined bya survey of the agitation which can be secured in the system in whichthe crude oil emulsion is being used. If the emulsion requires heat fortreatment, the bottles are placed in hot water bath, the length of timeand temperature determined by the particular plant equipment andpractice in which the particular emulsion is employed. If the plantprovides for hot agitation of the emulsion the bottles may be given acorresponding amount of manual hot agitation.

The bottles are then removed from the hot water bath and the water drop,presence of the bottom settlings (B.S.) layer and color and generalappearance of the oil are noted.

A thief grind-out is taken on all bottles which appear to be promising.A thief grind-out is made by preparing centrifuge tubes filled withgasoline to the 50% mark. The thief pipette is set to the proper lengthby adjusting the rubber stopper so that the bottom of the pipette isabout 4 inch above the oil-water level of the bottle with maximum waterdrop. This same setting is used for all subsequent thiefings onremaining bottles. The thiefed oil from each bottle is added to thecentrifuge tube to the 100% mark, and the tube is shaken. The samplesare then centrifuged for three minutes.

With certain paraflin base oils a portion of the paraffin is thrown downwith the B.S. If the centrifuge tubes are heated to 0 F the paraffinwill melt and be dissolved in the gasoline-oil mixture and usually willnot be thrown down again with the B.S. upon centrifuging while hot.However, occasionally the paraflin will re-congeal as the tube coolsduring centrifuging. If this occurs, the tube is removed from thecentrifuge and heated to 150 F. without shaking or disturbing thesettled B.S. layer. The heated sample is then centrifuged for 15seconds. This should give a true B.S. reading free of paraffin.

An excess chemical grind-out is then run on each centrifuge by addingseveral drops of a 20% solution in white gasoline or other solvent of achemical which causes complete separation of the Water and oil. Withsome sensitive emulsions the chemical will cause reemulsification. Inthese instances it is necessary to rethief and add a lesser amount. Eachtube is vigorously shaken to make sure that the packed B.S. layer isbroken up and the tubes heated to 150 F. in the case of troublesomeparaffin base crude oil. The samples are then centrifuged for threeminutes.

During the test the speed of the water drop is observed carefully afterthe emulsion-breaking chemical is added to the prescription bottles. Theobservation of the color and brilliance of the oil in transmitted lightis very important. In general, the brilliance and depth of colorincreases with a decrease in B.S. & W. (bottom settlings and water)content. The observations of color are made in the oil in theprescription bottles before and after heat treatment. In the idealtreatment of crude oil emulsions the oil-water line could be a sharp,clean line without any web or sludge present. Presence of a considerableamount of sludge or web is undesirable because this foreign materialwill eventually go to stock in the treating plant and be reported asB.S. Traces of web or sludge, however, will disappear or be removed inthe normal treating plant.

In almost all instances the thief grind-out and excess chemicalgrind-out readings indicate the formula that has most nearly producedcrude oil free from B.S. and water. The most efficient emulsion-breakingchemical is determined by the foregoing test procedure by the overallconsideration of the following factors: relative speed of the breakingof the emulsion which is usually indicated by speed of water drop, colorand brilliance of the oil layer, the relative absence of web or sludgeat oil-water line and the ability to most nearly produce treated oilthat is free from B.S. and water.

By way of illustrating the effectiveness of the emulsionbreakingchemicals contemplated by this invention, the composition of Example Iwas tested according to the foregonig bottle testing procedure onsamples of 22 gravity crude oil obtained from Smackover Field, Arkansas.The crude oil emulsion contained about 39% water. The commercialtreating chemical being used on the lease and the treating chemical ofExample I were both tested for comparative purposes. These treatingchemicals were added at a ratio of 0.10 part of a 10% solution, asdescribed in the foregoing procedure, to parts of the emulsion fluid.The samples were given 200 shakes cold. The observations made during thetests were recorded and are summarized in the following table.

TABLE I I Water Drop Thief Excess Treat ng Grind-Out Grind-Out Chemical1hr. 3%hr. 5hr. 22hr. B.S. Water B.S. Water Commercial Chemical 10 20 2632 0 9.0 0 9.5 ExampleI 9 27 29 35 Trace 6.0 O 6.0

120 F. A summary of the observations made during the test appears in thefollowing table.

The invention is hereby claimed as follows:

1. In a process for breaking petroleum oil emulsions of the water-in-oiltype, subjecting said emulsion to the action of a water-insolublecomposition comprising a substantially linear, hydrocarbon solventsoluble, alkyl phenol- -fonmaldebyde condensation product having about4-15 phenolic nuclei, wherein the alkyl phenol is at least 75%mono-alkyl phenol and the alkyl group has 4-15 carbons, saidcondensation product being substituted on the phenolic nuclei bypolyoxyalkylene radicals wherein the alkylene groups contain 2-3carbons, at least one of the polyoxyalkylene groups per molecule ofcondensation product being sulfated, the weight ratio of oxyalkylenegroups to said condensation product being in the range of 1:2 to 15:1,respectively, at least one hydroxyl group of the polyoxyalkylene groupsper molecule of condensation product being esterified with a dicarboxyacid and wherein substantially only one of the two carboxy groups of thedicarboxy acid is esterified.

2. The process of claim 1 wherein the dicarboxy acid is one having atleast 36 carbons.

3. In a process for breaking petroleum oil emulsions of the water-in-oiltype, subjecting said emulsion to the action of a water-insolublecomposition comprising a substantially linear, hydrocarbon solventsoluble, alkyl phenolformaldehyde condensation product having about 415phenolic nuclei, wherein the alkyl phenol is at least 75% mono-alkylphenol and the alkyl group has 415 carbons, said condensation productbeing substituted on the phenolic nuclei by polyoxyalkylene radicalswherein the alkylene groups contain 23 carbons, at least one of thepolyoxyalkylene groups per molecule of condensation product beingsulfated, the weight ratio of oxyalkylene groups to said condensationproduct being in the range of 1:2 to 9: 1, respectively, at least onehydroxyl group of the polyoxyalkylene groups per molecule ofcondensation product being esterified with a dicarboxy acid and whereinsubstantially only one of the two carboxy groups of the dicarboxy acidis esterified.

4. The process of claim 3 wherein the dicarboxy acid is one having atleast 36 carbons.

5. In a process for breaking petroleum oil emulsions of the water-in-oiltype, subjecting said emulsion to the action of a water-insolublecomposition comprising a substantially linear, hydrocarbon solventsoluble, alkyl phenolformaldehyde condensation product having about 415phenolic nuclei, wherein the alkyl phenol is at least 75% mono-alkylphenol and the alkyl group has 4-15 carbons, said condensation productbeing substituted on the phenolic nuclei by polyoxyethylene radicals ata weight ratio of polyoxyethylene radicals to condensation product inthe range of 1:2 to 2:1, respectively, at least one of thepolyoxyethylene radicals per molecule of condensation product beingsulfated, at least one hydroxyl group of the polyoxyethylene radicalsper molecule of condensation product being esterified with a dicarboxyacid and wherein substantially only one of the two carboxy groups of thedicarboxy acid is esterified.

6. In a process for breaking petroleum oil emulsions of the water-in-oiltype, subjecting said emulsion to the action of a water-insolublecomposition comprising a substantially linear, hydrocarbon solventsoluble, alkyl phenol-formaldehyde condensation product having about 4-15 phenolic nulcei wherein the alkyl phenol is at least 75 mono-alkylphenol and the alkyl group has 4-l5 carbons, said condensation productbeing substituted on the phenolic nuclei by polyoxyalkylene radicalsconsisting of a heterogeneous mixture of oxyethylene and oxypropylenegroups at a weight ratio of polyoxyalkylene groups to condensationproduct in the range of 1:2 to 15 :1, respectively, at least one of thepolyoxyalkylene groups per molecule of condensation product beingsulfated, at least one hydroxyl group of the polyoxyalkylene groupspermolecule of condensation product being esterified with a dicarboxy acidand wherein substantially only one of the two carboxy groups of thedicarboxy acid is esterified.

7. In a process for breaking petroleum oil emulsions of the water-in-oiltype, subjecting said emulsion to the action of a water-insolublecomposition comprising a substantially linear, hydrocarbon solventsoluble, alkyl phenolformaldehyde condensation product having about 4-15phenolic nuclei, wherein the alkyl phenol is at least 75 mono-alkylphenol and the alkyl group has 4-15 carbons, said condensation productbeing substituted on the phenolic nuclei by polyoxyalkylene radicals ata weight ratio of polyoxyalkylene groups to condensation product in therange of 1:2 to 15:1, said polyoxyalkylene radicals consisting ofpolyoxypropylene groups and polyoxyethylene groups substituted on thephenolic nuclei in sequential order, at least one of the polyoxyalkylenegroups per molecule of condensation product being sulfated, at least onehydroxyl group of the polyoxyalkylene groups per molecule ofcondensation product :being esterified with a dicarboxy acid and whereinsubstantially only one of the two carboxy groups of the dicarboxy acidis esterified.

8. In a process for breaking petroleum oil emulsions of the water-in-oiltype, subjecting said emulsion to the action of a water-insolublecomposition comprising a substantially linear, hydrocarbon solventsoluble, alkyl phenolformaldehyde condensation product having about 4-15phenolic nuclei, wherein the alkyl phenol is at least 75% mono-alkylphenol and the alkyl group has 4-15 carbons, said condensation productbeing substituted on the phenolic nuclei by polyoxyalkylene radicalswherein the alkylene groups contains 23 carbons, at least one of thepolyoxyalkylene groups per molecule of condensation product beingsulfated with sulfamic acid to form the ammonium salt of the sulfatedpolyoxyalkylated phenolformaldehyde condensation product, the weightratio of oxyalkylene groups to said condensation product being in therange of 1:2 to 15 :1, respectively, at least one hydroxyl group of thepolyoxyalkylene groups per molecule of condensation product beingesterified with a dicarboxy acid and wherein substantially only one ofthe two carboxy groups of the dicarboxy acid is esterified.

9. In a process for breaking petroleum oil emulsions of the water-in-oiltype, subjecting said emulsion to the action of a water-insolublecomposition comprising a substantially linear, hydrocarbon solventsoluble, alkyl phenol-formaldehyde condensation product having about 4-15 phenolic nuclei, wherein the alkyl phenol is at least 75% mono-alkylphenol and the alkyl group has 4-15 carbons, said condensation productbeing substituted on the phenolic nuclei by polyoxyalkylene radicalswherein the alkylene groups contain 2-3 carbons, at least one of thepolyoxyalkylene groups per molecule of condensation product beingsulfated with sulfamic acid to form the ammonium salt of the sulfatedpolyoxyalkylated phenolformaldehyde condensation product, the weightratio of oxyalkylene groups to said condensation product being in therange of 1:2 to 15:1, respectively, at least one hydroxyl group of thepolyoxyalkylene radicals per molecule of condensation product beingesterified with diglycolic acid and wherein substantially only one ofthe two carboxy groups of the diglycolic acid is esterified.

10. In a process for breaking petroleum oil emulsions of thewater-in-oil type, subjecting said emulsion to the action of awater-insoluble composition comprising a sub- 15 stantially linear,hydrocarbon solvent soluble, alkyl phenol-formaldehyde condensationproduct having about 4- 15 phenolic nuclei, wherein the alkyl phenol isat least 75% mono-alkyl phenol and the alkyl group has 515 carbons, saidcondensation product being substituted on the phenolic nuclei :bypolyoxyalkylene radicals wherein the alkylene groups contain 2-3carbons, at least one of the polyoxyalkylene groups per molecule ofcondensation product being sulfated with sulfamic acid to form theammonium salt of the sulfated polyoxyalkylated phenolformaldehydecondensation product, the weight ratio of oxyalkylene groups to saidcondensation product being in the range of 1:2 to 15:1, respectively, atleast one hydroxyl group of the polyoxyalkylene radicals per molecule 16of condensation product being esterified with 'maleic acid and whereinsubstantially only one of the two carboxy groups of the maleic acid isesterified.

References Cited by the Examiner UNITED STATES PATENTS 2,454,542 11/48Bock et a1. 260-53 2,454,544 1'1/48 Bock et a1 26053 2,541,994 2/51 DeGroote et a1. 252337 2,854,4'28 9/58 De Groote et a1. 260832 3,108,08710/63 Kirkpatrick et al. 260-49 JULIUS GREENWALD, Primary Examiner.

1. IN A PROCESS FOR BREAKING PETROLEUM OIL EMULSIONS OF THE WATER-IN-OILTYPE, SUBJECTING SAID EMULSION TO THE ACTION OF A WATER-INSOLUBLECOMPOSITION COMPRISING A SUBSTANTIALLY LINEAR, HYDROCARBON SOLVENTSOLUBLE, ALKYL PHENOLFORMALDEHYDE CONDENSATION PRODUCT HAVING ABOUT 4-15PHENOLIC NUCLEI, WHEREIN THE ALKYL PHENOL IS AT LEAST 75% MONO-ALKYLPHENOL AND THE ALKYL GROUP HAS 4-15 CARBONS, SAID CONDENSATION PRODUCTBEING SUBSTITUTED ON THE PHENOLIC NUCLEI BY POLYOXYALKYLENE RADICALSWHEREIN THE ALKYLENE GROUPS CONTAIN 2-3 CARBONS, AT LEAST ONE OF THEPOLYOXYALKYLENE GROUPS PER MOLECULE OF CONDENSATION PRODUCT BEINGSULFATED, THE WEIGHT RATIO OF OXYALKYLENE GROUPS TO SAID CONDENSATIONPRODUCT BEING IN THE RANGE OF 1:2 TO 15:1, RESPECTIVELY, AT LEAST ONEHYDROXYL GROUP OF THE POLYOXYALKYLENE GROUPS PER MOLECULE OFCONDENSATION PRODUCT BEING ESTERIFIED WITH A DICARBOXY ACID AND WHEREINSUBSTANTIALLY ONLY ONE OF THE TWO CARBOXY GROUPS OF THE DICARBOXY ACIDIS ESTERIFIED.